Results in Physics 47 (2023) 106334

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Results in Physics
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Dielectric relaxations and low dissipation factor with excellent temperature

stability of Ti1-x(Co1/3Ta2/3)xO2 ceramics
Theeranuch Nachaithong a, b, Narong Chanlek c, Pairot Moontragoon a, b,
Pornjuk Srepusharawoot a, b, Prasit Thongbai a, b, *
a
Giant Dielectric and Computational Design Research Group (GD–CDR), Department of Physics, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand
b
Institute of Nanomaterials Research and Innovation for Energy (IN-RIE), Khon Kaen University, Khon Kaen 40002, Thailand
c
Synchrotron Light Research Institute (Public Organization), 111 University Avenue, Muang District, Nakhon Ratchasima 30000, Thailand

A R T I C L E I N F O A B S T R A C T

Keywords: Low dissipation factor (tanδ) and excellent temperature stability of high dielectric permittivity are obtained in
Giant/Colossal permittivity Ti1-x(Co1/3Ta2/3)xO2 ceramics, which were prepared using a mixed oxide method. The unit cell of the rutile TiO2
Grain boundary barrier layer capacitor structure expanded due to relatively larger ionic radii of the co–dopants. The dopants homogeneously appeared
Impedance spectroscopy
in the microstructure of the TiO2 ceramics. Highly dense sintered–ceramics without second phase exhibit low
TiO2
tanδ of 0.015–0.043 with very high dielectric permittivities of 7.0–9.1 × 104 at 1 kHz. Notably, the temperature
Temperature coefficient
coefficient in the range of ±15 % was obtained in the temperature range of − 60–200 ◦ C. The electrically het­
erogeneous microstructure was studied using impedance spectroscopy. The contributions of extrinsic and
intrinsic factors were separated by the dielectric relaxations in low and high–frequency ranges, respectively. The
dielectric relaxations were well fitted using a modified Cole-Cole model. A low–frequency relaxation was well
described based on the Maxwell-Wagner relaxation model. A high permittivity was originated from the intrinsic
(i.e., defect dipoles) and extrinsic (internal barrier layer capacitor, IBLC) effects. A low tanδ was primarily caused
by the IBLC effect associated with a high resistance of the insulating part and defect dipoles.

Introduction Before the remarkable dielectric properties of these materials were

TiO2 is a very abundant material in nature and has many applications
for chemical, physical, optical, and electrical applications. For a
dielectric application, TiO2 was used classified as medium permittivity
materials with dielectric permittivity of ε′ ~ 90–200, which was used in
a high–power capacitor [1]. In recent years, the material development
intention of rutile TiO2 has transferred from a medium permittivity
material to its use as a high permittivity material with high ε′ ~ 104–105.
A large ε′ value of TiO2 is referred to as a giant dielectric response. The
dielectric properties (DPs) of TiO2 can be significantly changed by
doping process with alivovalent and/or isovalent ions [2,3]. Usually,
enhanced DPs with ε′ ~ 104 and low tanδ < 0.1 are obtained, while the
temperature coefficient for X–R standard applications (Δε′ < ±15 %) is
achieved in the range of − 55–180 ◦ C. Therefore, the DPs of TiO2 have
increasingly become the focus of research activity [2,4–9]. Accordingly,
TiO2 has a potential application in multilayer ceramic capacitors
(MLCCs) and related electronic devices [5].
discovered, CaCu3Ti4O12 (CCTO), which is in the ACu3Ti4O12 (A is
divalent or average divalent ions), is the most famous giant dielectric
ceramics. This material family showed ε′ ~ 103–105 values; however,
their tanδ values were higher than the standard applications [10–15].
Furthermore, it was likely that Δε′ < ±15 % was obtained only in a
narrow temperature range (− 55–100 ◦ C) [13,16–20]. Thus, it is hardly
to accomplish the significantly improved DPs from the CCTO–based
materials. Although a low tanδ value can be obtained in BaTiO3–based
materials, the Δε′ value is usually high near a curie temperature [21].
Furthermore, these materials are complex oxides, which are difficultly
prepared in a large scale compared to those of simple oxides (e.g., CuO,
NiO, and TiO2). Nevertheless, a tanδ value of NiO–based oxide was very
large even through its giant DPs can be achieved by co–doping with
aliovalent ions [22,23]. On the other hand, TiO2–based ceramics showed
a largely increased ε′ on the order of 104 and greatly reduced tanδ ≈
10− 2, which were performed by using aliovalent dopants of In3+ and
Nb5+ (InNbTO) [2]. TiO2 is a simple oxide and abundant material in

* Corresponding author at: Giant Dielectric and Computational Design Research Group (GD–CDR), Department of Physics, Faculty of Science, Khon Kaen Uni­
versity, Khon Kaen 40002, Thailand.
E-mail address: pthongbai@kku.ac.th (P. Thongbai).

https://doi.org/10.1016/j.rinp.2023.106334
Received 31 January 2023; Received in revised form 23 February 2023; Accepted 2 March 2023
Available online 6 March 2023
2211-3797/© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
T. Nachaithong et al. Results in Physics 47 (2023) 106334

nature. crystal structure and phase composition in the sintered specimens. As

It was reported that the DPs the InNbTO materials were changed
with the concentration of the dopant. The dielectric response increases
as the dopants changed from 0.05 to 10 %, while a low-frequency tanδ
slightly reduced. Furthermore, the dielectric response was also weakly
dependent on temperature and frequency. The comprehensive details of
the investigations of the DPs for many codoped TiO2 materials, such as
the Zn2+/Nb5+, La3+/Ta5+, Ga3+/Nb5+, Tm3+/Nb5+, Sc3+/Nb5+, Al3+/
Nb5+, Al3+/Ta5+, Zr4+/Sb5+, and etc. [3,24–31], were reported. Most of
them showed significantly improved DPs, as mentioned above. Form this
point of views, codoped TiO2 ceramics can be classified as a promising
material group with high potential for use in MLCCs and related devices.
For future application in a high technology, a low Δε′ (%) must be
extended to a wide temperature range (>150 ◦ C) as far as possible.
Unfortunately, a low Δε′ (%) of the InNbTO ceramics and many codoped
TiO2 ceramics was obtained only in a temperature range of ≤150 ◦ C,
which may be one of most serious problems supporting a high tech­
nology [32]. Hence, a new codoped TiO2 with improved Δε′ (%) over a
wide temperature range is important to seek. In addition, the important
cause causes of the observed DPs must be clarified. Electric dipoles from
complex defect clusters and space changes at the internal interfaces may
have impacts on the overall DPs in different temperatures
[2,4,24–26,33,34]. Each proposed model is reasonable from different
point of views, i.e., different temperature and frequency ranges.
Therefore, the objectives of this research are to seek a new codoped TiO2
that can exhibit improved DPs in all parameters and to ascribe the
important causes of the dielectric responses.
In this work, we synthesized a new codoped TiO2 system, i.e., Co2+
and Ta5+, employing a mixed oxide (MO) method. The crystalline
structure and microstructure were studied. Low tanδ values of
0.015–0.043 with very high ε′ of 7.0–9.1 × 104 were observed. Notably,
a low temperature coefficient was achieved over the temperature range
of − 60–210 ◦ C. The interfacial polarization and defect dipoles were
suggested to be the important causes of the DPs.
illustrated in Fig. 1(a), the XRD patterns provide the phase composition
data with a single phase of rutile TiO2 (JCPDS 21-1276) only for all the
samples. A slight difference in the XRD patterns of the CoTTO and TiO2
was found. To further clarify the possibility of the substitution of the
dopants into the TiO2 lattice, the lattice parameters were calculated. As
shown in Fig. 1(b), obviously, both the a and c values of the unit cell of
the CoTTO samples are larger than that of the undoped TiO2. Both values
also slightly increased with increasing x from 0.5 to 5 %. Both the ionic
radii of Ta5+ (r6 = 0.64 Å) and Co2+ (r6 = 0.65 Å) are larger than the Ti4+
(r6 = 0.605 Å) [35]. Therefore, the a and c values may be enlarged by the
substitution of the dopants, which was confirmed by linearly enlarged
cell volume of TiO2 with increasing the co–doping concentration [inset
of Fig. 1(b)]. Considering a single that was found in all the samples and
changes in cell parameters, both Co2+ and Ta5+ could be replaced Ti4+
in the rutile-TiO2 structure. It is important to note that a change in c
value was larger than that of a value. He et al. reported that, according to
the theoretical calculation and experimental results, the lowest energy
configuration of the InNbTO structure was obtained when the dopants
located along the c axis, resulting in a decreased c/a ratio. Thus, in this
work, it is possible that the Co2+ and Ta5+ doping ions preferred to
locate on the Ti4+ sites along the c axis.
To further characterize using other techniques and study the
dielectric properties, the valent states of all elements in the 1.0 %CoTTO
ceramic were examined, as displayed in Fig. S1 (supplementary infor­
mation). The minority of Ti3+ can be induced by doping with Ta5+
(Fig. S1(a)), as reported in previous papers [2,24,26,36]. Furthermore,
oxygen vacancies (VO⋅⋅ ) can be detected due to the charge compensation
for the replacement of Ti4+ with Co2+ or Co3+ (Fig. S1(b)), while the
presence of Ta5+ was confirmed. Details of the mechanisms of the
induced Ti3+ and VO⋅⋅ were explained in the supplementary information.

Experimental details

(Co1/3Ta2/3)xTi1-xO2 (CoTTO), where x = 0.005, 0.01, and 0.05,

powders were synthesized. These compositions are referred to as the 0.5
%CoTTO, 1.0 %CoTTO, and 5 %CoTTO, respectively. The starting raw
oxides, purchased from Sigma-Aldrich, consisted of rutile-TiO2 (>99.9
%), CoO (99.9 % purity), and Ta2O5 (99.99 %). Details of the experi­
mental steps for preparing codoped TiO2 ceramics are given in the our
previous works [26]. The calcination temperature was 900 ◦ C for 8 h.
The powders were further processed by pressing them into pellets, fol­
lowed by sintering at 1400 ◦ C for 5 h with heating rate of 2 ◦ C/min.
A field–emission scanning electron microscopy (FE–SEM) with
energy–dispersive X-ray analysis (EDS) (HITACHI SU8030, Japan) and
SEM–mapping technique, X-ray diffraction (XRD, PANalytical, EMPY­ a
REAN), A UV–vis Raman spectrometer (Horiba Jobin–Yvon T64000), c
and X-ray photoelectron spectroscopy (XPS) (PHI5000 VersaProbe II,
ULVAC–PHI, Japan) were employed to systematically characterize the
sintered specimens. Comprehensive details of each technique are pro­
a Å

c Å

vided in our previous published work [26].

Silver paint was selected as an electrode material. After painting Ag
V Å3

on both surfaces, the samples were heated at 600 ◦ C for 0.5 h. The
capacitance (Cp)–dissipation factor (or tanδ) mode was selected for the
dielectric measurement. The ε′ values were calculated using the
measured Cp values. The measurement was performed as a function of
frequency (40–107 Hz) and temperature (− 60–210 ◦ C) by employing a
KEYSIGHT E4990A Impedance Analyzer. Vrms = 500 mV was used
throughout the dielectric resting.
Fig. 1. (a) XRD patterns of the sintered 0.5 %CoTTO, 1.0 %CoTTO, and 5.0 %
Results and discussion CoTTO compared to that of the undoped TiO2. (b) Relationship of lattice pa­
rameters and doping levels; inset shows co-doping concentration dependence of
In this research work, we started with the characterization of the cell volume for CoTTO ceramics compared to that of the undoped TiO2.

2
T. Nachaithong et al. Results in Physics 47 (2023) 106334

It is worth noting that the XPS peak of Co cannot be detected in the XPS performed. Fig. 3(a) displays the Raman peaks of a pure TiO2 and all
spectrum of the 1.0 %CoTTO ceramic. For CaCu3-xCoxTi4O12 ceramics, CoTTO specimens. Four peaks of the Raman spectra confirm the rutile
the co–existence of Co2+/Co3+ was detected when the Co doping con­ TiO2 structure, which are similar to many co–doped TiO2 materials
centration was increased from x = 1.0 to 2.0. However, only Co2+ can [3,36,42]. Only the strongest A1g and Eg peaks were focused because the
be detected when x = 0.05 [37]. In this work, it is possible that a small A1g and Eg modes were used to describe the variations in O–Ti–O bonds
portion of Co3+ might also be formed when the co–doping concentration and VO⋅⋅ , respectively [42]. Thus, both modes might relate to the DPs of
increased. Nevertheless, both Co2+ and Co3+ can cause the formation of co–doped TiO2 materials [2–4]. The correlation between the Raman
VO⋅⋅ in the rutile–TiO2 structure, which was similar to other TiO2 codoped shifts of these two modes and doping level is illustrated in Fig. 3(b).
with acceptor (+2/+3)/donor (+5) dopants [2–4,26,38]. On the other Obviously, the Raman peak of Eg mode appeared at lower wave numbers
hand, the co–existence of Co2+/Co3+ in CCTO ceramics caused an in­ as the codoped concentration increased from x = 0 to 5 %. Nevertheless,
crease in the giant DPs due to the enhanced mixed–valent structure of
Co2+/Co3+. This might also be responsible for the CoTTO ceramics.
Usually, the DPs of ceramics and their microstructures have a close
relation together [12,18,39]. Thus, the morphologies of the sintered
specimens were focused. As revealed in Fig. 2, no pores are observed in
the microstructure for all samples even at the grains and grain bound­
aries. The existence of all elements in the CoTTO ceramics were
confirmed using the EDS technique, as shown in Fig. S3(a) of supple­
mentary information. We also found that the dopants were well
dispersed throughout the microstructure using the SEM–mapping tech­
nique, as shown in Fig. S3(b). The average grain sizes (G) of all the
CoTTO samples slightly changed with G values of 10.6 ± 3.5, 7.3 ± 2.3,
and 10.9 ± 4.0 μm for the 0.5 %CoTTO, 1.0 %CoTTO, and 5.0 %CoTTO,
respectively. According to the previous works [26,40], the G of TiO2 was
greatly reduced by doping with Ta5+. Thus, the G should be significantly
reduced. However, a slightly changed G of the CoTTO ceramics was
observed, which was likely attributed to the dominant effect of Co2+
doping ions. The grain growth in polycrystalline ceramics is usually
determined by diffusion of atom or ions across the grain boundary.
Enhanced diffusion of ions can be primarily resulted from the formation
of liquid phase or increased point defect concentration (vacancies).
However, the melting point of CoO and eutectic temperature of
CoO–TiO2 are much higher than the sintering temperature of the CoTTO
ceramics [41]. Thus, the dominant effect of the Co2+ on the retained
grain size of the CoTTO ceramics may be attributed to the increase in
defect concentration. Doping TiO2 with Co2+ ions resulted in the crea­
tion of VO⋅⋅ , following:

(1)
TiO2
CoO ̅̅̅→ CoTi + VO⋅⋅ + OO

Thus, it is likely that during the sintering process, the enhanced

diffusion of VO⋅⋅ , which was confirmed to exist using the XPS technique
(Fig. S1(a)), is the key factor for contribution of the grain growth. The
restorative and driving forces acting on the grain boundary, which were
resulted from the Ta5+ and Co2+ dopants, were balanced, and hence the
G of the CoTTO ceramics slightly changed. In the other word, the
reduced G of the Ta5+–doped TiO2 was inhibited by the Co2+ doping
Fig. 3. (a) Raman spectra the sintered 0.5 %CoTTO, 1.0 %CoTTO, and 5.0 %
ions.
CoTTO compared to that of the undoped TiO2. (b) Relationship between the
To further confirm the existence of VO⋅⋅ the Raman spectroscopy was Raman shift (Eg and A1g models) and doping level.

Fig. 2. Surface morphologies of (a) 0.5 %CoTTO, (b) 1.0 %CoTTO, and (c) 5.0 %CoTTO using SEM technique.

3
T. Nachaithong et al. Results in Physics 47 (2023) 106334

according to Eq. (1), the primary cause of this observation is likely the Table 1
Co2+. The A1g peak position slightly shifted to a higher wave number, The ε′ and tanδ values at ~25 ◦ C and 1 kHz and temperature coefficient (Δε′ (%))
which was attributed to the variations in Ti–O stretching and O–Ti–O at the temperatures − 60 and 200 ◦ C.
bond bending due to the dopants. Parker et al. [43] demonstrated that x%CoTTO ε′ tanδ Δε′ (%)
the Eg peak of TiO2-x move backward from 447 to 437 cm− 1 as x = 0.02. − 60 ◦ C 200 ◦ C
The theoretical value of x in the 5.0 %CoTTO (in the cause of no self­
0.5 %CoTTO ~70,700 0.017 − 2.68 % 12.9 %
–charge compensation between Co2+–2Ta5+) is 0.017, the Eg peak
1.0 %CoTTO ~79,500 0.015 − 3.41 % 12.1 %
decreased from 447.5 (pure TiO2) to 435 cm− 1, which is consistent with 5.0 %CoTTO ~91,900 0.043 − 9.73 % 14.3 %
that reported by Parker et al. The Eg peak shifting to lower a wave
number showed the presence of more VO⋅⋅ in the CoTTO compared to that
of the undoped TiO2.
To explain the origin of enhanced DPs on the CoTTO ceramics, the
influence of the co–dopant concentration on the ε′ and tanδ at different
frequencies was studied. As illustrated in Fig. 4 and its inset, the ε′ in the
frequency range of 40–104 Hz of the CoTTO increases with co–dopant
content from 0.5 to 5.0 %. The step–like decrease in ε′ was observed at
the frequency higher than 104 Hz. This result was due to the relaxation
mechanism of a low–frequency dielectric response, which was likely due
to the extrinsic effect. tanδ in the frequency range of 40 to 106 Hz is
illustrated in the inset of Fig. 4. tanδ peak was observed in a high­
–frequency range, corresponding the appeared step–like decrease in ε′ .
The values of ε′ and tanδ at 1 kHz were listed in Table 1. Notably, all the
samples showed a very high ε′ of 7 × 104 with low tanδ values of
0.015–0.047. The excellent DPs of the CoTTO are comparable to those
reported in the (Ga3+/Ta5+) [26], (Ga3+/Nb5+) [34], (Zn2+/Nb5+) [44],
(Sc3+/Nb5+) [25], (In3+/Nb5+) [2,32,33], and (Al3+/Nb5+) [42] co- f
doped TiO2.
Fig. 5. Frequency dependence of ε′ in the temperature range from − 60 to 0 ◦ C
According to the extrinsic effects (i.e., interfacial polarization at in­ for 5 %CoTTO. Symbol and solid curve are the experimental data and fitted
ternal interface and resistive outer surface layer), a very large dielectric curves fitted using Eq. (2), respectively. Inset shows the Arrhenius plots of τlow− f
response of ε′ ~ 104 is generally obtained in a low–frequency range, for all CoTTO.
especially when the temperature decreased [11]. The dielectric response
due to the intrinsic effect can occur at a relatively low–temperature
range [2,4,34]. It is important to note that the contribution of i-GBs
′ ′
Δεlow− f Δεhigh− f
ε* = (2)
′

(IBLC) or electrodes is usually very high [45]. Thus, the electrode effect
( )α + ( )β + ε∞
1 + iωτlow− f 1 + iωτhigh− f
must be separated from the IBLC effect. Generally, the electrode effect
on the dielectric response is dominant at low frequencies and high where Δεlow−
′
and Δεhigh−
′
are the dielectric strengths in low (extrinsic
f f
temperatures. In this work, we tried to separate the dielectric responses
effect) and high–frequency (intrinsic effect) ranges, respectively, which
between the extrinsic (IBLC) and intrinsic effects by represent the DPs at
are estimated to be the contributions of the dielectric responses in these
low temperatures from − 60 to − 10 ◦ C, as illustrated in Fig. 5. Unfor­
two ranges. We set ε∞ ≈ 250 [2], which is the contribution from the
′

tunately, at the lowest measured temperature of − 60 ◦ C, a large

dielectric response due to the intrinsic response was entirely observed.
Thus, we fitted the data using the modified Cole–Cole equation, using
two dielectric relaxation parts:
atomic (Pa ) and electronic (Pe ) polarizations in a rutile TiO2. τlow− f and
τhigh− f are the relaxation times in low and high–frequency ranges,
respectively. The data in a low–frequency range was well fitted by the
first term of Eq. (2). The data in a high–frequency range was fitted in
accordance with the second and third terms using τhigh− f ≈ 1.0–0.71 ns
and β = 1, as the temperature increased from − 60 to 0 ◦ C with a given
activation energy for a high relaxation of Ea,high− f ~ 30 meV for co–do­
ped TiO2 [2,34]. As illustrated in Fig. 5, the dielectric data were well
fitted by Eq. (2). According to the fitted curves in a low–frequency range,
τlow− f values of all the samples at the selected temperatures were ob­
tained with α ≈ 0.80–0.87. As displayed in the inset of Fig. 5, the tem­
perature dependence of τlow− f followed the Arrhenius law,
( )
Ea
τlow− f = τ0 exp (3)
kB T

where T is absolute temperature and kB is Boltzmann constant, τ0 is a

constant. According to the fitted results, the activation energy (Ea )
values required for dielectric relaxation in a low–frequency range
(Ea,low− f ) of the 0.5 %CoTTO, 1.0 %CoTTO, and 5.0 %CoTTO can be
calculated and found to be 77, 91, and 113 meV, respectively. The Ea
increased as the co–doping content increased. It is observed that the Ea
values of the CoTTO ceramics are similar to those reported in CCTO
(93–109 meV [46,47]), Bi2/3Cu3Ti4O12 (91–95 meV [10,46]), Y2/
3Cu3Ti4O12 (90 meV [46]), and La2/3Cu3Ti4O12 (80 meV [46]). The DPs
Fig. 4. ε′ as a function of frequency at ~25 ◦ C for 0.5 %CoTTO, 1.0 %CoTTO,
of these materials were well described using the Maxwell–Wagner
and 5.0 %CoTTO; inset shows tanδ as a function of frequency at 30 ◦ C.

4
T. Nachaithong et al.
relaxation (MWR) model based on the interfacial polarization (Pi ) at the
internal interface (or internal barrier layer capacitor, IBLC). Thus, it is
likely that the dielectric response in a low–frequency range was caused
by the extrinsic effect due to Pi .
As shown in the inset of Fig. 5, τlow− f of the CoTTO ceramics increases
with increasing the codoping concentration, corresponding to their
tanδ–peak positions [inset of Fig. 4] and the frequency at which the
step–like decrease in ε′ appeared. When the average τlow− f was short­
ened, the polarization can be occurred in a higher frequency range.
According to the MWR model [10], it was theoretically demonstrated
that the τlow− f was dependent on the semiconducting grain (semi-G)
resistance (Rg) and insulating grain boundary (i–GBs) capacitance (Cgb),
τlow− f ≈ Rg Cgb (4)
To describe the dielectric relaxation behavior, an impedance spec­
troscopy was performed. Generally, the electrical responses of the sem­
i− G and i− GBs are determined by small and large semicircular arcs,
respectively [10,39]. If a small arc cannot be observed, the electrical
response of semi− G can also be determined by a nonzero intercept on the
Z′ -axis [39]. Fig. 6 illustrates impedance complex plane (Z*) plots of all
the CoTTO at 30 ◦ C. Only parts of a large arc were observed in all
CoTTO, while small semicircular arcs were observed in the 1 %CoTTO
and 5 %CoTTO. As shown in the inset of Fig. 6, a nonzero intercept was
observed in the 0.5 %CoTTO. These results clearly indicated that semi-G
and i-GBs were produced in the TiO2 codoped with Co2+ and Ta5+.
Accordingly, Pi can be induced under al applied electric field, giving rise
a large dielectric response in a low-frequency range. This is the first
reason proving the extrinsic effect. Considering a small arc and nonzero
intercept in Z* plots, Rg of the CoTTO increased with increasing
codoping content. As shown in Fig. 4, the ε′ value below 104 Hz
increased as the codoping concentration increased, indicating the
enhanced Cgb value. From Eq. (4), the increased τlow− f was well described
by the MWR model via the increased Rg and Cgb values. This is the
second reason for confirming the contribution of extrinsic effect in the
CoTTO. The surface layer effect in the CoTTO can be ignored because
both sides of the outer surface layer of the CoTTO were removed before
making electrodes for the dielectric measurement. Therefore, the IBLC
was the primary effect on the low− frequency dielectric response.
It is worth noting that a low-frequency relaxation due to the extrinsic
effect in the CoTTO is similar to those observed in conventional giant
dielectric oxides (CGDO) [10,22,39,48]. However, the totally different
behaviors between them are relatively high− frequency responses. The
dielectric response due to the intrinsic effect in CGDO usually give rise to
the ε′ value of ~102 in a high− frequency range and low temperatures.
semi
semi
Fig. 6. Z* plots at 30 ◦ C of all CoTTO; inset reveals an expanded view near the
origin, showing the nonzero intercept on Z′ -axis for the 0.5 %CoTTO.
5
Results in Physics 47 (2023) 106334
Nevertheless, as illustrated in Fig. 5, it is likely that the dielectric
response due to the intrinsic effect in the CoTTO can give rise to the ε′
value of 2.0 × 104, as well as observed in other codoped TiO2 systems
[2,4,38]. Many research works believed such a dielectric response was
attributed to the defect dipoles [2–4,38,44]. According to Eqs. (1) and
(S1–S3) in supplementary information, many defect dipoles can be
formed, i.e., Ti4+ − e− − VO⋅⋅ − Ti4+ − e− , VO⋅⋅ − VTi − VO⋅⋅ ,Ta⋅Ti − Ti4+ − e− , and
CoTi − VO⋅⋅ . Furthermore, the complex defect clusters of
CoTi − VO⋅⋅ +2Ta⋅Ti +2TiTi may also formed and have a great impact on the
overall DPs, which can be active even at a high− frequency range and at
low temperatures. These defect dipoles were referred to as the electro­
n− pinned defect dipoles (EPDDs), which can be referred to as the
intrinsic effect. A very large dielectric response with ε′ ~ 104 can be
extended into a high− frequency region by this way. Thus, the signifi­
cantly decrease in the ε′ associated with the frozen of polaron [49]. It is
worth noting that EPDDs were suggested to be the important cause of the
giant DPs in some codoped TiO2 systems [2,3,38]. The formation of
EPDDs was dependent on the ionic size of the acceptor dopants [34],
which were formed in the In3+/Nb5+ and In3+/Ta5+ codoped TiO2
systems [2,4] due to a relatively large ionic radius of In3+ (r6 = 0.80 Å)
[35]. When the ionic radius of the acceptor dopant was not large enough
or smaller than that of the host Ti4+ (e.g., Al3+ (r6 = 0.535 Å) or Ga3+ (r6
= 0.62 Å)), the EPDDs were not created in the Al3+/Nb5+ [42] and
Ga3+/Nb5+ [34] codoped TiO2 systems. Considering the ionic radius of
Co2+ (r6 = 0.65 Å), it is possible that the EPDDs can be formed in the
CoTTO ceramics, which can contribute to the total dielectric response.
Besides very high ε′ and low tanδ values, the temperature depen­
dence of the DPs is also one of the key factors for considering a dielectric
material for applications. The temperature coefficient of the ε′ at 1 kHz
(Δε′ (%)) at any temperatures was calculated. As shown in Fig. 7,
Notably, the Δε′ (%) values of all the CoTTO samples were less than ±15
% in the temperature range from − 60 to 200 ◦ C. Usually, the Δε′ (%)
values of many CGDO materials rapidly increased as the temperature
increased higher than 150 ◦ C. As summarized in Table 1, at 200 ◦ C, the
Δε′ (%) values of the 0.5 %CoTTO, 1.0 %CoTTO, and 5.0 %CoTTO were
12.0, 12.1, and 14.3 %, respectively. The Δε′ (%) values of the CoTTO
can meet the standard values for the X7R, X8R, and X9R capacitors. The
ε′ and tanδ values at ~25 ◦ C and 1 kHz of the 1.0 %CoTTO ceramic were
compared to those of other giant dielectric oxides. As summarized in
Table 2, it is suggested that the CoTTO ceramics can be considered as
one of the most interesting giant dielectric oxides. A low tanδ was pri­
marily caused by a very large resistance of the i− GBs, as shown in Fig. 6.
Furthermore, confinement of free electrons in defect clusters can also be
a cause of a low tanδ.
Fig. 7. Temperature coefficient of ε′ at 1 kHz for all CoTTO.
T. Nachaithong et al. Results in Physics 47 (2023) 106334

Table 2 org/10.1016/j.rinp.2023.106334.
The ε′ and tanδ values at ~25 ◦ C and 1 kHz of the 1.0 %CoTTO compared to
those of other giant dielectric oxides. References
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